Halogenated phosphorus esters, and process for preparing them



- midochloridates, the

3,132,169 Patented May 5,

' V 3,132'1'69 s HALoGENATED PHosrHoRUs ESTERS, AND t f PRooEss Fon PREPARWG rrmM Gail H.Brum, James L. Schwendeman, and Richard Anderson, Dayton, Ohio, assigos to Monsanto Chemical Company, St. Louis,l Mo., a corporation of Delaware l NoDra'Wing. Filed Sept. 26,1960, Ser. No. 58,192

'The'present invention provides new and valuable organic compounds of phosphorus, the method of producing 4the same, and synthetic resinous compositions comprising theA new compounds as modiers therefor. r

' According to the invention there are provided certainV esters of pent'avalent phosphorus acids, which esters contain both chlorine and bromine, and which are selected from the class consisting of (I.) phosphorobromidochloridates of the formula t n ,Y in which R is selected from the class consisting of hydrogen and alkyl and haloallryl radicals of from lto 2 carbon atoms, R is selected from the class consisting of hydrogen and alkyl and haloalkyl radicals of from 1 to 5 carbon -atoms-*and n is zero or one, and (II) a phosphate of the wherein R,.R and n are as above dened and R". is selected from the class consisting of R and hydrocarbyloxymethyl radicals of from 1 to 8 carbon atoms, and Vwherein one R" at a pair of adjacent carbon atoms must be hydrogen. Y

The starting material which is employed for preparing the above-dened phosphorobromidochloridates and phosphates is a,2chloro1,3,2-dioxaphospholane compound or Va 2chloroj1,3,2-dioxaphosphorinane compound of the i' wherein R, R and n are as defined above. Compounds of this formula are readily obtained, in known manner, by reaction of phosphorus trichloride With a 1,2- or 1,3-

alkanediol or a halogen-substitution product thereof.

For preparing the presently provided phosphorobro- 2-chloro-l,3,2-dioxaphospholane compound or the 2-chloro-1,3,2-dioxaphosphorinane compoundV is reacted with bromine. Thereby the cyclic structure is--cleaved, and an atom of bromine adds to either end of the resultingrchain, thus:

The phosphorobromidochloridates are Vstable, welldeiined compounds which may be employed for a'variety of industrial purposes, e.g., as gasoline additives, as cross? linking agents for polymers, and as modifyingag'ents for cellulosic materials and starches. According to theinvention, however, they are very conveniently employed for the preparation of phosphates having two lbromfinecontaining ester radicals and one chlorine-containing ester radical. This is achieved by treatingthe phosphorobro-Y midochloridates with an oxirane compound, eg., ethylene oxide and certain mono-substitution products thereof; The reaction takes place bycleavage of. the oXirane ring and bonding of the cleaved A I I O-Co chain thrzoughipxygen .tothe kPhosphorus atom of the' v phosphorobromidochloridate,V the b'romine and 'chlorine The above compound jis `that which is obtainedwhen the oxirane ring opens between the oxygen atom and the CHR portion ofthe ring. However,-the'oxirane ring can open also between the oxygen atom" and the CH2' portion ofthe ring. In that case, the phosphates obtained from the phosphorobromidochloridates and theV oxirane compound have the formula IIL "lla' Ilz o CHZBr Bro (IJ- ooPooHR/f VR'YRMrHR" Y t f 'cnzo1 (B) The ratio of (A) to (B) in the product will depend upon: the nature of the oxirane compound and of the reaction conditions. Product A generally predominates, especially under catalytic conditions and/or when R" is a bulky substituent. However, since both (A) and (B) are usefull for substantially the same applications, the presence of both types of ester products in the phosphorobromidochloridate-oxirane reaction product/does not generally require isolation of either.

As stated above, the starting materials which are used for preparing the present phosphorobromidochloridates are either 2-chloro-l,3,2-dioxaphospholane compounds which may be prepared from the reaction of phosporus trichloride andthe 1,2-diols, orV the 2chloro-l,3,2dioxa phosphorinane compounds which may be prepared fromv said chloride and diols of the formula 2-chloro-1,3,2-dioxaphospholane from ethylene glycol, 2-chloro-4-methyl-1,3,2-dioxaphospholane from propylene glycol,-

Zlclrloro-@S-dirnethyl-1,3,2-dioxaphospholane from 2,3,-

-but-anediol,

diol, 2-chlor'o-4,5diethyl1,3,2-dioxaphospholane from 3,4-hexianediol, f 2chloro-4,4dimethyl1,3,2-dioxaphospholane from 2- methyl-1,2-pr`opanediol, 2-chloro4,4,5,5-tetramethyl-l,3,2-dioxaphospholane from ,v 2,'3-dimeth y1-2,3butanediol, Y 2-chloro-4-iodomethyl-l,3,2-dioxaphospholane from 3- iodo-1,2propanediol, Y l Y 2-chloro-4,4,5-triethyl-l,3g2-dioxaphospholane from 3-ethyl-3,4hexanediol, 2-chloro-1,3,2-dioxaphosphoninane from 1,3-propanediol, 2chloro5butyl-S-ethyl-1,3,Z-dioxaphosphorinane from Z-butyl-Z-ethyl-l,3-propanedio1, Y 2-chloro5,5dimethyll,3,2fdioxaphosphorinane from 2,2-

dimethy1-1,3-propanediol, 2-chloro-4-ethyl-6-methyl-1,3,2-dioxaphosphorinane from 2,4-hexanediol, 2-chloro-4,4,6-trimethy141,3,2-dioxaphosphorinane from Z-methyl-ZA-pentanediol, v 2-chloro-4- (Z-bromoethyl) -l ,3,2-diox-aph0sphorinane from 5bromo-l,3pentanediol, 2-c-hloro-4- (truoromethy-l) -l ,3 ,Z-dioxaphosphorinane from 4,4,4-trifluoro-1,3-butanediol, 2-chloro-4-pentyll,3,Z-'dioxaphosphorinane from 1,3-octanediol, 2-chloro-5 ,S-bis( chloromethyl) -1 ,3 ,2-dioxaphosphorinane from 2,2-bis(chloromethyl)1,3propanediol;

Phosphorobromidochloridates which 'are obtained by reacting the 2-chloro-1,3,2-dioxaphospholane compound are -bromoalkyl or -bromohaloalkyl phosphorobromidochloridates, e.g., bromination of 2chloro-l,3,2-dioxa phospholane yields 2-bromoethyl phosphorobromidochloridate. Those obtained from the 2-chloro-l,3,2dioxa phosphorinanes have the bromine atom in the fy-position, i.e., reaction of 2-chloro-1,3,2-dioxaphosphorinane with bromine yields B-bromopropyl phosphorobromidochloridate. The following `table shows other phosphorobrornidochloridates which are Obtained by bromination of substituted 2-chl'oro-1,3,2-dioxaphospholanes:

substituted 2lchloro-l,3,2 Phosphorobrornidochlordate 4,4,5,5tetramethyl Z-bromo-l,1,2-trimcthylpropyl.

4-chlorornethyl 2-bromo-l-(chloromethyl)ethyl.

4,5-b1s (Z-ehloro eth yl) 2-bromo-4-chloro-l- (fl-chloroethyl) butyl.

4,*1l-cl1ethyl 2-bron1olethylbutyl 4,4,5,5tetrakis(chlor 2bromQ-3-chloro1,1,2tris (chloromethybpropyl. 4-othyl75-iluoromethyl Q-bromo-B-fluoro-lv-ethyl-propyl. 4,4,5-tr1ethyl 2-bromo-l,l-diethylbutyl.

4-(2bromoethyl) 3-bron1o-1-(bromomethyD-propyl. 4-ethy1 1-(bromomethyDpropy1.

substituted 2chloro1,3,2 Phosphorobromidochloridate obtained dioxaphosphorinane ars-ammi 4,5,6-trimethyl. 5chloromethyl 4,4-dimcthy1 a-bromo-i,l-dimethyipmpyl.

5-(triliuoromethyl) 3-bro1no21(trifluoromethyD-propyl. S-butyl--eth yl Z-bromornethyl-2-ethylhexyl. 5-(2-iodoethy1) Z-brornomethyl-tiodobutyl. 4,4,6-trimcthyl 3-brorno-l,l-dimethylbutyl.

4,5,5,6tetrarnethyl 4-etl1yl5-chloroethyl 5,*5-bis (chloromethyl) In order to prepare the presently provided mixed phosphates from lche phosphorobromdochloridates, the latter are contacted with `an oxirane compound, i.e., ethylene oxide `or a substitution product thereof in which one of the hydrogen atoms is replaced by an alkyl or lhaloalkyl radical of from* 1- to 5 carbon atoms or by a hydrocarbyloxymethyl radical Iof from l to 8 carbon atoms. A few examples of useful oxiran'e compounds are propylene oxide, epichlorohydrin, phenyl glycidyl ether and butadienemonoxide. Other examples are shown in the following table of new phosphates which are obtained according to the invention by reaction of the indicated phosphorobromidochloridate with the indicated oxirane compound, with cleavage of the oxirane ring occurring between the oxygen and the substituted carbon atom.

'5* v Ys Ialready stated, the nature of the ester which is obtained by reaction of fthe phosphorobromidochloridate depends upon Ithe point at which cleavage of the oxirane ring occurs. Since :there is la preferential'tendency for cleavage to occur between the substituted carbon atom and oxygen, the products are predominantly the -bromo ,A9-chloro esters of fthe types shown above =for Z and X. However, there is generally also Iformed varying proporftionsof the isomen'c productswhich result by cleavage Y of the roxirane ring between the oxygen atom and the unsubstituted carbonv atom. For example, in lthe third preparation of the above table wherein 2-bromo-1-methylethyl phosphorobromidochloridate is reacted with propylene oxide, in addition to the Z-bromo-Lmethylethyl 2-bromopropyl 3-chloropropyl phosphate which is shown inthe table, there are also formed isomers such as CH3 o omni Brouzbno-P-ooncrr,

OCHCHs CHzCl 1 Similarly the third from last preparation of the above table, in addition to the phosphate shown therein, Le., -bromo-Z-methylpropyl 2-'bromo-3cyclohexyloxypropyl Z-chloro-3-cyclohexyloxypropyl phosphate, there are also formed such isomers as "o oHBBr CH3 OCHzOHoICHzOCy wherein Cy` denotes the cycloheXy-l radical.

In view of the above, it will be apparent that the invention provides a facile method of preparing numerous phosphates having both chlorine and bromine as sub.

stituents in the epoxide-denived portions of the phosphorus esters. The 2chlorol,3,2-dioxaphospholane compounds `and the 2-chloro-1,3,2-dioxaphospho1inane compounds are readily available starting materials, since they are easily prepared from the 1,2- or 1,3-diols and'phosphorus tn'chloride.-

. Awaluable aspect of the invention provides la method for vpreparing the phosphates, without isolation of any intermediately formed productst lby starting with the diol :and the phosphorus itrichloride. We have 'found that reaction of the diol with a phosphorus ftrichl-oride proceeds readily in the absence of a diluent or solvent. This permits using the reaction product obtained from the diol and the phosphorus trichloride, without tedious isolation, in the subsequent bromination step. Dispensing with the diluent or solvent also improves the yield of the phospholane or phosphorinane. Hence, a presently preferred Vmethod comprises the fol-lowing steps: The diol Vand the phosphorus trichloride are mixed together in substantially equimolar proportions in [the absence of a solvent or diluent until cessation of hydrogen chloride evolution, the resulting reaction mixture is treated with bromine until cessation of ybromine decolorizaition, and the brominat-ion product thus obtained is reacted with the oxii'ane compound to give the mixed phosphate. This can all be etected in one reaction vessel, and without isolating any intermediate' products. The mixed phosphate thus obtained may be used directly -for al variety of Yindustrial or agricultural purposes; but if desired, the

phosphate product may -be purified, eg., by washing with aqueous alkali and water, or by distillation.

In' the rst step, when working in lthe absence of exi `traue-ous diluents or solvents, reaction proceeds readily and usually without the application of external heating.

Isolationzof thephospholane or phosphorinane is not re' quired because reaction of the glycol with the phosphorus trichloride proceeds substantially to completion; likewise, 4the. bromination and the subsequent reaction with the oxira-ne compound proceeds so smoothly and :completely 'that there is no occasionior the presence of appreciable quantities of materialsiother thanithe'desired 'phosphate product in the iin-al reaction mixture. Since the bromination and the oxirane reaction both involve addition, n0 byproduct formation is involvedg`|and because both reactions iare easily carried to completion, no separation of unconsumed reactants is necessitated; An important aspect of the present invention is thus the method of preparing mixed phosphates which comprises addition of bromine to a cyclic phosphorus compound of the formula wherein R is selected from the .class consisting of hydrogen and alkyl and haloalkyl radicals of from 1 to 2 carbon atoms, R is selected from the class consisting of hydrogen and alkyl and haloalkyl radicals of trom 1 to 5 carbon atoms, and n is an integer of zero or one, until cessation of bromine discoloration,land then treating the resulting reaction product with an oxirane compound ofv :the formula mogen-RH' wherein R is selected from the class consisting of R and hydrocarbyloxymethyl radicals of from 1 to 7 car` bon atoms 'and wherein one` R at a pair of adjacent carbon atomsmust be hydrogen.

Ot course, if desired, the presently provided Vmixed phosphates can l,also be prepared `by starting 'with the phosphorobromidochloridates. This is particularly advantageous when it is desired to prepare a number of dit'.-v terent kinds of esters having one common Ialcohol residue,` i.e., that which is present in the phosphorobromidochloridate. Thus, 2-chloro-'1,3,2-dioxaphospholane can be fbrominated to give a large stockl of 2-'bromoethy1 phosphorobromidochloridate which can then be stored and convented at any time to various phosphates by reaction With an oxirane compound.` For example, lreaction of the' Zabromoethyl phosphorobromidochloridate with ethylene oxide gives bis(Z-bromoethyl) 2-chloroethyl phosphate;`

with phenyl fglycidyll ether it gives predominantly 2- bromoeth'yl 2bromo`3phenoxypropyl Z-chloro-laphenoxypropyl phosphate; and with butadiene monoxide it ygives predominantly 2-bromoethyl 2-bromo-3-butenyl 2-Y chloro-3-butenyl phosphate. An important aspect of the invention is thus the provision of a process for the prep-V experimental runs, the reactionl may be moderated byV When cooling or by the use of an inert liquid diluent.

mole of bromine, these reactants are advantageously used f in such stoichiometric proportions. An excess ot either reactant can be used, of course, since such an excess would involve only the necessity'of removing the unreacted material from the bromination product.

The presently provided phosphorobromidochloridates are stable, well-characterized compounds which are advantageously employed for purposes other than for the preparation of mixed phosphates. The chlorine and bromine atoms which are attached to the phosphorus atom are both very reactive; hence esters may be prepared therefrom by reaction with alcohols or thiols, and phosphoramides by reaction with amines. The chlorine and bromine atoms display diierent degrees of reactivity, so that'in many instances partial estersor amides are obtained. The phosphorobromidochloridates are also advantageously employed as treating agents for cellulosic materials and other substances having a plurality of hydroxy groups, e.g., polyvinyl alcohol, and the sugars and starches.v Reaction of the phosphorobromidochloridatesv with such materials generally imparts flame-proofing properties thereto and, depending upon the nature of the individual phosphorobromidochloridate, and the material treated therewith, there will be obtained, in addition to the flame-retardance, an improvement in hand and feel, crease-resistance, etc.

As stated above, the phosphorobromidochloridates are particularly valuable asstarting materials for the production of mixed phosphates containing both bromine and chlorine. Reaction of the phosphorobromidochloridates'Y withvethylene oxide, or the other oxirane compounds disc losed above, to give the mixed esters generally proceeds substantially quantitatively; and since the reaction is one of addition, here again, as in the case of the phosphorobromidochloridate preparation, there is involved no formation of by-products. Since production of the triorgano phosphate involves addition of two moles of the oxirane compound to one mole of the phosphorobromidochloridate, these reactants are advantageously used in such stoichiometric proportion; however, an excess of the alkylene oxide may -be used because any unreacted material can be separated from the desired phosphate product. In some instances it may be advantageous to react the phosphorobromidochloridate with an equimolar amount of one epoxide, and then to complete the reaction by use of a different epoxide; or other than equirnolar quantities of the two epoxides may be employed.

Reaction oi the phosphorobromidochloridate with thev oxirane compound to give the presently provided phosphates proceeds at ordinary, decreased or increased temperatures and inthe presence orV absence of catalysts, eg., a Lewis acid. The use of catalysts is preferred in that reaction time is thereby very substantially decreased, use of lower reaction temperature is facilitated,V and yields of phosphate product are materially improved. As catalysts there may be employed, e.g., such compounds as titanium tetrachloride, zirconium tetrachloride, aluminum chloride, ferrie chloride, boron tritluoride, tin tetrachloride, iron lings, ammonium metavanadate, phosphorus trichloride, phosphorus tribromde, pyridine, tri-n-butylamine, quinoline, aniline, N,Ndiethylaniline, etc. Inert liquid diluents may or may not be employed. The reaction is generally conducted at moderately elevated ternperatures; but depending upon the nature of the individual reactants and upon the nature of catalyst, temperatures of, say, from C. to'lOO" C. may be used. The addition reaction is generally exothermic; hence in initial runs it is advisable to employ external cooling. Heating maybe required to assure completion of the reaction andmay be desirable throughout the reaction when using the less reactive, higher alkylene oxides or when operating either inthe absence of a catalyst or in the presence of catalyst materials of comparatively low eiciency. The selection of the proper operating temperature as related to nature lof reactants, catalyst andthe quantities thereof can easily be arrived atby one skilled in the art.

The Vpresently provided mixed phosphates are useful for a variety of industrial purposes, e.g., as fuel additives, lubricant additives and as solvents. They are particularly usefulV as modifiers for natural and synthetic polymeric materials. The present phosphates possess a high degree of utility as ilame-retardants for polymeric materials. At the same time, depending upon the quantity of the mixed ester which is in contact with the polymer, plasticizing or softening effect is obtained. Thus, at, say, a 10% to %V concentration of the phosphate, basedy on the total of polymer and phosphate, the polymer generally not only is ilame-proofed but also plasticized. Use-of the present phosphates at much lower concentrations, say, in an amount which is Vsome cases is as low as 1.0%, provides many polymeric systems with reduced burning rates. The present phosphates may be used with the polymers in a quantity which is equal to that of the polymer, but in most instances favorable results with respect to improvement in flame-retardance and/ or plasticity is obtained at concentrations which are dern'tely lower. It will be evident, of course, that for the preparation of plastisols, quantities of the phosphate which are greater than that of the polymer will be required. Use of the present phosphorus compounds with the polymeric materials in quantities which confer benecial properties to the polymers with respect to a desired effect, eg., flexibility in the case of a iilm, darne-proofing in the case of foam insulators and extruded iibers or molded pieces, often confers to the polymer an improvement also in such characteristics as resistance to impact, dimensoinal stability, moldability, etc. These varied effects are readily determinable by those skilled in the art simply by visual observation or by use of conventional techniques. Hence in order to arrive at optimum benecial-effect suited to the purposesfor which the polymeric composition is designed, only routine testing, involving variation of adjuvant quantity, is generally required, although in some instances one or more members of the whole class of the presently provided phosphates will be found to impart a degree of modication at a low concentration which can be attained by other members of the Y prepared from the natural polymers.

class at significantly higher concentrations.

Fibrous cellulosic products are prime examples of the natural polymericl materials which are advantageously modified by the present phosphates. This includes products made of cotton, linen, regenerated cellulose, kapok, hemp, wood and wood pulp, eg., textiles, twines, paper, cardboard, pressed board, batting wood iiour, sawdust, etc. Another group of natural polymers of carbohydrate origin includes the starches such as those derived from corn, barley,potatoV and cassava. Another class of natural polymers with which the Ypresent phosphates are beneficially used are the natural gums, eg., agar, gum arabic, psyllium seed, tragacanth and gum karaya. YNatural rubber is also included. Natural resins modified by the present phosphates include shellac, copal, damar, pine balsam, rosin, etc. Proteinaceous polymeric materials, e.g., animal glue, casein, wool and leather are also advantageously modied by said phosphorus compounds. The natural polymeric products, generally, are rendered flameretardant when contacted with the present phosphates in appropriate proportions, and worthy` of special comment is the glow-proofing of readily ignitible dusts and powders Plastici/zing effect is conferred by the present phosphates to those of the polymers which lack the degrees of softness and ilexibility that. are required in the applications for which the pol- Y ployed may v polypropylene,

polymer; polymerized acrylyl and alkacrylyl compounds modified according to the invention are those obtained from a polymerizable monomer compound having ethylenic unsaturation.

A particularly preferred class consists of the polymerized vinyl and vinylidene compounds, i.e., those having the YCH2i radical. Compounds having such a radical are,e.g., the solid polymeric alkenes, such as polyethylene,

polyisobutylene or ethylenepropylene cosuch as acrylic, chloroacrylic and methacrylic acids, anhydrides, esters, nitriles and amides, for example, acrylonitrile, ethyl or butylacrylate, methyl or ethyl methacrylate, methoxymethyl or 2-(2-butoxyethoxy)ethyl methacrylate, 2-(cyanoethoxy)ethyl 3-(3-cyanopropoxy)propyl acrylate or methacrylate, Z-(diethylamino) ethyl or 2- chloroethyl acrylate or methacrylate, acrylic anhydride y* or methacrylic anhydride; methacrylamide or chloroacryl-r amide, ethyl or butyl chloroacrylate; the olenic aldehydes such as acrolein, methacrolein and their acetals; the vinyl and vinylidene halides such as vinyl chloride, vinyl linoride, vinylidene fluoride and l-chloro-l-fluoroethylene; polyvinyl alcohol; the vinyl carboxylates such as vinyl acetate, Vinyl chloroacetate, vinyl propionate, and vinyl 2-ethylhexanoate; the N-vinyl imides such as N-vinylphthalimide and N-vinyl-succinimide; the N-vinyllactams such as N-vinylcaprolactam and N-Vinylbutyrolactam; the Vinyl aromatic hydrocarbon compounds such as styrene, r-methylstyrene, 2,4-dichlorostyrene, aor -vinylnaphthalene, divinylbenzene and vinylfluorene; the vinyl ethers such as ethyl vinyl ether or isobutyl vinyl ether; vinyl-substitutecl` heterocyclic compounds such as vinylpyridine, vinylpyrrolidone, vinylfuran or vinylthiophene; the vinyl or vinylidene ketones such as methyl vinyl ketone or isopropenyl ethyl ketone; vinylidene cyanide; etc. Homo-V polymers of the above compounds or copolymers or terpolymers thereof are beneficially modified by the present phosphates.

Examplesof such copolymers orterpolymers are those obtained by polymerization of the following monomer mixtures: vinyl chloride-Vinyl acetate, acrylonitrile-vinylpyridine, styrene-methyl methacrylate; styrene-N-vinylpyrrolidone, cyclohexyl methacrylate-vinyl chloroacetate, acrylonitrile-vinylidene cyanide, methyl methacrylate-vinyl acetate, ethyl acrylate-methacrylamideethyl chloroacrylate, vinyl chloride-vinylidene chloridevinyl acetate, etc.

Other `presently employed polymers of compounds having the ethylenic group, C=C are the homopolymers, `copolymers and terpolymers of the ff-olefnic dicarboxylic acids and the derivatives thereof such as the anhydrides, esters, amides, nitriles and imides, e.g., methyl, 'butyl, 2-ethylhexyl or dodecyl fumarate or maleate, maleic, chloromaleic, citraconic or itaconic anhydride,`

fumaronitrile, dichlorofumaronitrile or citracononitrile,

, fumaramide, or maleamide; maleimide or N-phenylmaleimide, etc. Examples of particularly useful copolymers and terpolymers prepared from the -olefinic dicarboxy f compounds are the copolymers of maleic anhydride and v a vinyl compound such as ethylene, propylene, isobu-tylene, styrene, -methylstyrene, vinyl acetate, vinyl propionate, methyl isopropenyl ketone, isobutyl vinyl ether, etc.,

the copolymers of dialkyl fumarate such as ethyl or butyl fumarate and a vinyl compound such as styrene, vinyl acetate, vinylidene chloride, ethyl methacrylate, acrylonitrile, etc.`

carbonate with ethylenic compounds such as ethylene,y

`vinyl chloride, vinyl acetate, 1,3-buta-die-ne, acrylonitrile, methacrylonitrile, or the esters of methacrylic or acrylic acid.

Advantageously modified by the present phosphates are also polymers, copolymers or terpolymers or polymerizable compounds having a plurali-ty of double bonds, e.g., a rubbery, conjugated diene polymerizate such as homopolymerized 2,3-butadiene, 2-chlorobutadiene or isoprene and linear copolymers or terpolymers such -as butadiene-acrylonitrile copolymer, isobutylene-but-adiene copolymer (butyl robber) butadiene-styrene copolymer or 2 chlor-obutadiene vinylidene cyanide-acrylonitrile terpolymer; esters of saturated dior polyhydroxy compounds with olenic carboxylic acids such as ethylene glycol dimethacrylate, triethylene glycol dicrotonate or glyceryl triacrylate; esters of olefinic alcohols with dicarboxylic acids or with oletinic-monocar-boxylic acids such as diallyl adipate, divinyl succinate, diallyl fumarate, allyl methacrylate or crotyl acrylate and other diethylenically unsaturated compounds such as diallyl carbonate, divinyl ether or divinylbenzene, as Well as the cross-linked polymeric. materials such as methyl methacrylate-diallyl methacrylate copolymer or butadiene-styrene-divinylbenzene terpolymer.

Polymerized materials prepared by subsequent reaction of the preformed Ivinyl polymers@ e.g., polyvinyl alcohol, the polyvinyl acetals such as polyvinyl formal or polyvinyl butyral, or completely or partially hydrolyzed polyacrylo-l nitrile, are likewise modified in properties by the present phosphates to give polymeric materials of enhanced utility.

Polymeric materials with which the present phosphates can be employed as adjuvants are also polymers which contain elements such as sulfur, phosphorus, boron or silicon, elg., the sulfides, /sulfones, sulfoxides, sulites, sulfates and sulfonates such as thepolymers and copolymers of vinyl sullide, 'vinyl sulfone, Z-propenyl sulfoxide, ethylene sul-fonic acid and its sa1ts,esters and amides, and sul- Ifonated polystyrene; the olefin-sulfur `dioxide polymers,

the phosphines, phosphites, phosphates and phosphonates such as diphenylvinylphosphine, allyl phosphite and methphane, Irayon, regenerated r-ayon, etc. The phosphorus' compounds may be incorporated into hns of such cellulose derivatives by adding them to the solutions Ifrom which the tilms are cast or into the melts from which the fibers are extruded.

The present phosphates are particularly suited-to the modilication of liquid resin compositions of the polyester type, e.g., the linear polyesters which are obtained by theY reaction of one or more polyhydr-ic alcohols with one lor combination with one or more saturated polycarboxylic acid compounds, or the cross-linked polyester resins lwhich are obtained by reacting the linear polyester with a compound containing a CH2=C` group.

The cross-linking component of the presently modified polyester resin may be, e.g., styrene, the nuclear or sidechained substituted styrenes such as 3,4-dichlorostyrene, a-chlorostyrene, u-methylstyrene; other vinyl-substituted yhydrocarbons such as aor -vinylnaphthalene or 4-vinyll l biphenyl; the olefinic carboxylic acids and the esters, nitriles, amides and anhydrides thereof such as acrylic acid, methacrylic acid, ethyl acrylate, or acrylonitrile; the vinyl esters such as vinyl acetate or vinyl chloroacetate; the l olelinic ketones such as ethyl vinyl ketone and isopropenyl methyl ketones; the alkenes such as `isobutylene and 2- pentene; the olenic ethers such asfyinyl ethyl ether and vinyl isobutyl ether; etc. y

The epoxy resins are another class of polymeric materials with which the present compounds are compatible andare advantageously used. These resins are condensation products yformed by the reaction of a polyhydroxy compound and epichlorohydrin, which condensation productsare subsequently cured by addition of cross-linking agents. The hydroxy compound may be, e.g., ethylene glycol, 4,4isopropylidenediphenol, etc. The cross-linl ing agent employed in the curing or hardening `step may be a dicarboxylic compound suchas phthalic anhydride or adipic acid, but is more generally a polyamine such as ethylene diamine, mor p-phenylene diamine or diethylenetriamine. Y Y

The polyurethanes comprise another class of polymeric materials which are beneficially modified by the present phosphates. The polyurethanes, like the fabovementioned polyesters, are commercial materials which are employed in structural applications, e.g., as linsulating -foams, in the manufacture of textile fibers, as resin bases `in the manufacture of curable' coating compositions andas impregnating adhesives in the Ifabrication of laminates of woods and other librous materials. Essentially the polyurethanes are condensation products of a diisocyanate and la compound having a molecular Weight of at least 500 and preferably about 150G-5000, and at least two reactive hydrogen atoms, ie., hydrogen atoms determinable by the Zerewitinoff method. The useful active-hydrogen containing compounds may be polyesters prepared from polycarboxylic acids and polyhydric alcohols, polyhydric polyalkylene ethers havingrat least 2 hydroxy groups, polythioether glycols, polyesterarnides, etc.

The polyesters or polyesteramides used for the production of the polyurethane may be branched and/ or linear, e.g., the esters of adipic, sebacic, 6-amino-caproic, phthalic, isophthalic; terephthalic, oxalic, malonic, succinic, maleic, cyclohexane-l,Z-dicarboxylic, cyclohexane-l,4di carboxylic, polyacrylic, naphthalene 1,2 dicarboxylic, fumarie, itaconic, etc., with polyalcohols such as ethylene glycol, diethylene glycol, pentaglycol, glycerol, sorbitol, triethanolamine, di-(-hydroxyethyDether, etc. and/ or amino-alcohols such as ethanolarnine, aminopropanol,V

4-aminopropanol, S-aminopentanol-l, 6-aminohexano1, IO-aminodecanol, -amino-S-methylhexanol-l, p-hydroxymethylbenzylamine, etc.; and with mixtures of the above polyalcohols and amines, ethylene diamine, hexamethylene diamine, 3-methylhexamethylene diamine, decamethyiene diamine and m-phenylenediamine etc. and/ or amino-alcohols, etc.V In the esterication, the acid per se may be used for condensation or, where desirable, equivalent components such as the acid halide or anhydride may be used.

vThe alkylene glycols and polyoxyalkylene or polythioalkylene glycols used for the production of the polyurethanes may comprise ethylene glycol, propylene glycol, butylene glycol-2,3, butylene glycol-1,3, 2-methylpentanediol-2,4, 2-ethylhexanediol-l,3, hexamethylene glycol, styrene glycol and decamethylene glycol, etc, and diethylene glycol, triethylene glycol, tetraethylene glycol, polythioethylene glycol, polyethylene glycols 200, 400 and 600, etc., dipropylene glycol, tripropylene glycol, trithiopropylene glycol, polypropylene glycols 400, 750, 1,200 and 2,000, etc. t

Broadly, any of the polyesters, polyisocyanate-modiiied polyesters, polyesteramides, polyisocyanate-modied polyesteramides, alkylene glycols, polyisocyanate-modifled alkylene glycols, polyoxyalkylene glycols and polyisocyduction of the polyurethanes.

anate-modied polyoxyalkylene glycols, etc. having free reactive hydrogen atoms, free reactive carboxylicv and/or especially hydroxyl groups may be employed for the pro- Moreover, any organic compound containing at least two radicals selected from the class consisting of hydroxyl and carboxyl groups may be employed.

The organic polyisocyanates useful for the production of the polyurethanes include ethylene diisocyanate, ethylidene diisocyanate, propylene-l,2-diisocyanate, butylene- 1,3-diisocyanatc, hexylene-l,6diisocyanate, Vcyclohexylene-1,2-diisocyanate, m-phenylene diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 3,3di methyl-ll-,4'biphenylene diisocyanate, 3,3'-dimethoxy4,4 biphenylene diisocyanate, 3,3diphenyl4,4biphenylene diisocyanate, 4,4biphenylene diisocyanate, 3,3-dichloro 4,4'biphenylene ydiisocyanate, triphenyl methane triiso- Y cyanate, 1,5-naphthalene diisocyanate or polyisocyanates Y guanidine,

in a blocked or inactive form such as the bisphenyl carbamates of toluylene diisocyanate, p,pdiphenylmethane diisocyanate, p-phenylene diisocyanate and 1,5-naphthalene diisocyanate, etc.

For preparation of the dame-retardant polyurethanes, the present phosphorus compounds are preferably added to a mixture of the reactants and catalyst before hardening.V The hardened molded pieces or foams are rendered flame-retardant by the inclusion therein of the phosphate in quantities'of, say, from 2% to 25% by weight of the polyurethane. Simultaneous piasticizing property is evidenced and continues to be demonstrated until the quantity of phosphate is substantially equal to that of the polyurethane. Use of the present phosphates in the polyurethane foams can'also increase dexibility and, in some applications, improve the mechanical properties of the foams. n

Phenolic resins are also beneicially modified by the present phosphates, which compounds are incorporated into the resin either by milling in molding applications or by addition to hlm-forming or impregnating and bonding solutions previous to casting. Phenolic resins with which the present compounds are employed are, for example, the phenol-aldehyde resins prepared from phenols such as phenol, cresol, xylenol, resorcinol, 4-butylphenol, 4-phenylphenol, and aldehydes such as formaldehyde, acetaldehyde, or butyraldehyde in the presence of either acidic or basic catalysts, depending upon whether the resin is intended for use as a molding or extruding resin or as the resin base in coating and impregnating compositions. V

' The aminoplasts comprise another group of aldehyde resins which are beneficially modified by the present phosphates. Examples thereof are the heat-convertible condensation products of an aldehyde with urea, thiourea cyanamide, dicyandiamide, alkyl or aryl guanamines, and the triazines such as melamine, 2chloro-4,6- diamino-1,3,5triazine and 2-hydroxy-4,6diamin`o1,3,5- triazines. The present adjuvants are compatible with the aminoplasts; and depending upon the quantity of phosphate used, they serve to plasticize them,V and to render them fire-retardant. When the aminoplasts are destined for use as impregnating agents, bonding adhesives, coatings and casting of ilms, the phosphorus compounds are incorporated intoy solutions or suspensions in which the aminoplast is carried. VThe resulting mixtures give strong, lire-retardant laminates when sheets of paper, glass Vcloth or fabric are impregnated therewith and cured.

. are obtained dame-retardant, dye receptor, and/or plasticizing effects.

o prepared, c g., by reaction of N-carbobenzyl oxyglycin with glycine or a mixture of glycine and lysine, or an N-carboxy amino acid anhydride such as N-carboxy-DL- phenylalanine anhydride; the polymeric lactarns, eg., polycaprolactam, piperidone, 2-oxohexamethyleneimine and other cyclic amides. The present phosphates can beinl corporated into molding or extruding compositions for plasticizing and flame-retardant eifect and/or to serve. as mold lubricants.

The present phosphates are also advantageously employed as adjuvants for polymeric aldehydes, e.g., homopolymeric, high-molecular weight formaldehyde.

The present phosphates are also adjuvants for linear polymers obtained by the self-condensation of' bifuncf tional compounds generally, e.g.the polyethers which are derived by the self-condensation of dihydric alcohols such as ethylene glycol, propylene glycol or hexamethyl# ene glycol;Y the polyesters which are obtained by the selfcondensation of hydroxy acids such as lactic acid or 4f hydroxybutyric acid, the polyamides which are prepared by the self-condensation of amino carboxylic acids such as 4-aminobutyric acid or -aminocaproic acid; theV polyanhydrides which are formed by the self-condensation of d dicarboxylic acids such as sebacic acid or adipic acid, etc.`

The present'phosphates are plasticizing flame-retardants for such self-condensation products, generally; and Where transparentizingeiect and dye receptivity are lacking, the phosphates are often instrumental in ameliorating such deliciencies.

The Ypresent vmixed phosphates are likewise advantageously employed with the silicone resins, i.e., the linear polymers which have the repeating unit: l i i 'i -SIi-O--Si-O-S'i-O- T T T Where T denotes an organic radical such as the methyl or,..phenyl radical, as well as the cross-linked modifications thereof, e.g., cross-linked polymeric divinyltetra. methyldisiloxane. The present phosphates haveV a beneflcial effect on the mold shrinkage properties and the dimensional stabilities of the thermo-setting polymers and also yimpart plasticizing and transparentizing effects.Y -In bonding and laminate applications tensile strength prop, erties of the siloxane resins are improved.

Theinvention is further illustrated by, but not limited to, the following examples:

Example 1 4To 1221 g. (9.66-moles) of 2chlorol,3,2 dioxaphos.v pholane there Was added 1521.5 fg. of bromine (to the point of persistent bromine color) duringa time of 0.7

hour while maintaining the temperature of the reaction.

mixture at -20 C. by Dry Ice cooling. A 9.5 g.por. tion-ofthe reaction mixture wassubmitted for nuclear magnetic resonance study; a phosphorus chemicalshift was "observed at |14.9 relative to H3PO4. Another 95.5

i4 130 ,CL/i ama. tqgiveas residue 3419 g. (98.2% of 'theory based on the 2-chloro-1,3,2-dioxaphospholaue) of the substantially pure bis(2bromoethyl) 2-chloroethy1 Y phosphate, 111325 1.5003. Distillation of a 253 g. portion gave 229.7 g., B.Pl 180-182 =C./0.1 mm., which analyzed as follows: v

This example shows preparation of bis(2bromoethy1) 2-chloroethyl phosphate on a larger scale.

To 2,532 g. (20.0 moles) of `2-chloro1,3,2-dioxapl1ospholane there was added during 0.8 hour 3151 g. of bromine while maintaining the Atemperature of the reaction mixture at 10-25 C. The rate of addition was determined bythe rate of: heat removal, since the bromine reacted instantaneously. A 6;5g. sample Was removed for NMR study. It had a chemical shift of +15.1 p.p.m. whichjis characteristic of 2-bromoethyl phosphorobromidochoridate.

The remainder of the bromination product was warmed to IC. and 6 g. oftitanium tetrachloride catalyst-Was added thereto. A total ofVV `1810 g. of ethylene oxide was passed into the resulting mixture in 3 hours as the temperature was allowed to rise to 120 C. Another 120 g. of the oxide was introduced while applying heat to maintain the temperature at 11S-121 C. When the total g. portion `of the reaction mixture was. distilled through a 6 column to give 91,1 g. of the substantially pure 2- bromoethyl phosphorobromidochloridate, B P.. 81.

C./0.2 mm. nD2-5 1.5225.

The remainder of the bromination product vobtained Vabove was warmed to 50 C. and 4.1 g. of titanium tetrachloride wasradded thereto to serve as catalyst for sub-., Addition of thel oxide Was started at 50 C. and during passage of 770 sequent reaction with ethylene oxide.

g. of the oxide into the reaction mixture the temperature rose to 62 C.y It was allowed to increase to 90 C. asV

another 82 g. of the oxidev was added, and nally to a temperature of C. as the'remainder of the total v 900g. of oxide was added. The whole was maintained at 10S-120 C. for 0.75 hour and then concentrated to 1930- g. ofV oxidehad been added, the reaction mixture was concentrated to C./ l mm. to give as residue 7,283 g. (97.3%'theoretical yield based on the phospholane) of the substantiallyvpure bis(2bromoethyl) 2- chloroetliyl phosphate; NMR chemical shift, +1.7 ppm.; 111325 1.5004; d2525-1.7797; and analyzing as follows:

. Found Cale/d for CuHizBrzClOiP Percent C.V 19. 62 19. 24 Percent H 37 3. 23 Percent Br-. 42. 40 42. 75 Percent Clt. 9'. 26 9. 46 Percent P--- 8 10 8.28

- Example 3 i Io 84.3,g`{ `(0.50 mole) of 2chloro-5,5fdimethyl1,3,2- dioxaphosphorinane there wasgra'dually'added duringl 0.25 hour 80.5 g. (101% of theory) of bromine while maintaining the reactionmixture at a temperature of 10-20 C.,by means of Dry I ce cooling. At the end lof thatftime a 7.0jg. sample was removed for analysis and another 41 g. of the reaction mixture was distilled to give 37.9 g. of the substantially pure 3-bromo2,2dimethyl propyl phosphorobromidochloridate, B .P.`92-94 C./ 0.05

mm., which analyzed as follows; i g

. Found Calcd for CsHioBrClOzP rerc'entBLp; Q "49.03 .Y 48.7" Percent 01.. 11.15 10.8 Percent P d.' 9.57 .9.44

The remainder of the bromination product was warmed to 40 C., 5 drops ofV titanium tetrachloride was added, and to thev resulting mixture there was introduced 50.7Y

' g. (0.874 mole, 25% excess) of propyleneoxide during a timeof 0.3 hour. Approximately the first half of the oxide was added at 50-60 C., employing cooling. The remainder, which was added without cooling,. ,was introduced atl a rate which caused Vrapid reflux (6U-75 C.).'

follows:

Found Calcd for CnHzQBrzClO? Percent o 29. ss 29. 7'0 Percent H 4. 79 4. 98 Percent Br 36. 24 36. 00 Percent Cl v 7.77 7.97 Percent P 6.87 6.97

Example 4 To an ice-cooled solution consisting of 126.5Y g. (1.0 mole) of 2chloro1,3,2-dioxaphospholane in 100 g. of

0.2 hour, 159.8 g. (1.0 mole) of bromine. During the addition of the bromine, the temperature of the reaction mixture was 5-10 C., and the bromine was decolorized as rapidly as it was added. An 8.0 g. sample of the Areaction mixture was removed for nuclear magnetic resonance study. It was thus determined to be 2-bromoethyl phosphorobromidochloridate, the chemical shift for phosphorus which was observed being a major Apeak at .7 ppm. (relative to H3PO4) To the solution containing 2-bromoethyl phosphorobromidochloridate which remained after withdrawal of the 8.0 g. sample, there was added 5 drops of titanium v carbon tetrachloride there was added, during a time of V3,132,1ee

. 165 v covered) to give as residue 4151.5 g. (97.3% theoretical yield) of the substantially pure 2-bromoethyl 2-bromo- 3-chloropropyl 2,3-dichloropropyl phosphate, a yellow liquid which analyzed as follows:

Found Calc'd for CgHnBrzClsOrP Percent C 20.19 20.4 Percent II... 3.00 3. 0 Percent Br 33. 37 34. 0 Percent Cl 22.756 22.6

Example 6 the monoxide had been added, the whole was maintained,

tetrachloride and then, during 0.3 hour, there was introduced tothe resulting mixture 121 g. (2.09 mole, 4.5% excess) of propylene oxide. During addition of the oxide, cooling was employed to maintain the temperature of the reaction mixture at -55 C.v When all of the propylene oxide had been added and cooling had been discontinued, the reaction mixture warmed spontaneously to reux and reachedV a maximum of 62 C. in `0.2 hour. It was then warmed to 100 C. within 1.5 hours. After removal of an analytical sample, about 100 ml. of benzene was added, the solution was washed with water, dried over CaClz, and concentrated to 100 C./0.1 mm. to give as residue 247 g. of substantially pure 2-bromoethyl 2-bromopropyl 2-chloropropyl phosphate having a single characteristic phosphorus NMR chemical shift at +33 ppm. (relative to H3PO4).

Example 5 Bromine was introduced during a time of 0.6 hour into 126.5 g. (1.0 mole) of 2-chloro-1,3,2-dioxaphospholane while maintaining the temperature of the reactionV mixture at 5 -20 C. by means of Dry Ice cooling. Essentially 1.0 mole of bromine was employed, all of this quantity being rapidly decolorized by the dioxaphospholane.

To the 2-bromoethyl phosphorobromidochloridate there was added 10 dropsl (about 1 g.) of titanium tetrachloride and to the resulting mixture there was added during 0.2 hour at a temperature of -65 C., 194 g. (2.1 moles, 5% excess) of epichlorohydrin. Mild'cooling was employed while the reaction mixture was subsequently maintained at 'l0-75 C. for 0.25 hour and at 80-85 C. for another 0.2 hour.y When there was no further evidence of exothermic reaction, the reaction mixture was warmed at 95-105 C. for 0.75 hour and then allowed to stand overnight at room temperature. At the end of that time it was concentrated to a pot temperature of 130 C./0.1 mm. (whereby 18.0 g. of colorless liquid, probably largely unreacted epichlorohydrin,Y was rewith cooling, at 7 0-80 C. for 0.2 hour and then gradually allowed to reach a temperature of 101 C. spontaneously. When there was no further evidence of exothermic vreaction, the mixture was warmed to 120 C. and nally concentrated to 120 C./ 0.1 mm. to give as residue 435 g. (95% theoretical yield) of a mixture of phosphates consisting essentially of 3-bromo-Z,2-dimethylpropyl 2-bromo- 3-buteny1 2-chloro-3-butenyl phosphate and a minor proportion of Vthe isomeric 3-bromo-2,2-dimethylpropyl 1 bromomethyl 2-propenyl 1-chloromethyl-Z-propenyl phosphate. v

Example 7 Bromination of 2-chloro-4-(chloromethyl)-1,3,2dioxa phospholane was eflected by passing 51.5 g. (0.32 mole) K 2-bromo-3-chloropropyl phosphorobromidochloridate.

To the product prepared above there was added 0.4 g. of ammonium metavanadate as catalyst for conversion to phosphate, and 97.7 g. (0.65 mole, 5% excess) of phenyl glycidyl ether was added to the resulting mixture at a rate to maintain the temperature at -100 C. with cooling. When addition was completed, the whole was kept at -100 C. until heat of reaction had diminished. The reaction was then completed by warming at C. for 0.3 hour. After standing overnight it was kconcentrated to 130 C./0.2 mm. to give as residue 199.5 g. of phosphate product consisting essentially of 2-bromo-l-(chloromethyl)ethyl 2-bromo-3-phenoxypropyl 2-chloro-3-phenoxypropyl phosphate together with minor amounts of isomeric 2-bromo-3-chloropropyl 2-bromo- 3-phenoxypropyl 2-chloro-3-phenoxypropyl phosphate, 2fbr0mo-1-(chloromethyl)ethyl 1(bromomethyl)2phe noxyethyl l-(chloromethyl)-2-phenoxyethyl phosphate and 2-bromo-3-chloropropyl 1- (bromoethyl)2phenoxy ethyl 1-fchloromethyD-2-phenoxyethyl phosphate.

Example 8 This example shows preparation of bis(2bromoethyl) 2-chloroethyl phosphate by reaction ot ethylene glycol with phosphorus chloride to give 2chloro-l,3,2dioxa Yphospholaue, reaction of the latter with bromine and subsequent reaction of the brominated product with ethyleneY Y oxide.

To 433 g. (3.15 moles) of phosphorus `trichloride cooled to 12 C. there was added during 1.0 hour 186.2 g. (3.0 moles) of ethylene glycol.

was required to maintain the temperature of the reaction n Percent P land, any funreacted phosphorus trichloride. Vsample ofthe Z-chloro-1,3,2-dioxaphospholane thus obtained was removed -for study and the remainder of the' mixture below C. When all of the glycol had been introduced, the colorless reaction mixture was stirred aty K14-17 C. :for about 0.1 hour, placed under water pump vacuum, and nallywarmed at reflux (47 C.) for 0.3

hour in order to remove bly-product hydrogen chloride product'was cooled as bromine was added thereto until decolorization wasA- no `longer obtained. A. total of '454 g. (95% of theory) of bromine was thus added during v0.4 hour at 15-20" C. The reaction mixture thus ob-l tained was substantially-pure Z-bromoethyl phosphorobromidochloridate. A 6 g. sample thereof was removed for analysis, and 15 drops oftitanium tetrachloride was added to the remainder to serve as catalyst 'for subsequent re- Only slight coolingl A 5.0 gj,

- 'contained a'ction of the 2-bromoethyl phosphorobromidochloridate with ethylene oxide. A total of 270 g. of the oxide was introduced with a slow stream of nitrogen below the liquid surface over a period of 0.9 hour.

70 C., and the last 70 g. was added while the temperature was allowed to climb to 110 C. When all of the ethylene v oxide had been added, the whole was warmed at 95-1 10 C. for an additional 0.5 hour. It was then concentrated to 130 C./0.01 mm. to give as residue 1030 g. (97.6% of` theory based on the bromineor 92.7% based on the ethylene glycol) of the substantially pure bis(2bromo ethyl) 2-chloroethylv phosphate which analyzed as follows:

Found Caled for CnH12B12ClO4P Percent C 19.23 19.24 `Percent; H 3.36 3.23 Percent Br- 42. 99 4. 75 Percent Cl 9.19 9.46 8. 50 8. 28

` Nuclear magnetic resonance study of the phosphate gave akcharacteristic peak of l-l.7 p.p.m. relative to H2PO4.

. Example 9 lThis example shows the use-of a crude non-distilled i 'Y chloro-1,3,2-dioxaphospholane for preparation of phosphate via the phosphorobromidochloridate and washing of the phosphate product to remove impurities introduced in thek initially used phosphola-ne. l

2-bromoethy1 phosphorobromidochloridate was prepared by adding 928.5 g. (5.81 moles) of brornne to 760 g. (6.0 moles) of crude"'2chloro1,3,2-dioxaphospholane during Ia time of 0.4'l1our while maintaining the temperature of the reaction mixtureat l0-20 C. with Dry'lce teeming. Y

Y ,'I'he 2bromoethyl phosphorobromidochloridate thus obl The first 100 g. of the.Y oxide was added at 55-60 C., the second 100 g. at 60- ethyl)` chloroethyl phosphate. Purification was, elected by washing a 600 g. portion of the crude phosphate, first with two 200 g. portions of 5% aqueous sodium bicarbonate and then twice with water. The product was dried by concentrating to 100`C./0.5 mim. rlfihere was thus obtained 556 g. of the substantially pure bis(2-bromo' ethyl) 2-chloroethyl phosphate having an NMR chemical shift at +19 ppm., relative to H3PO4.

i Example I0 Finely ground polystyrene was blended with either bis 4iI(2-bromoethyl) 2chloroethyl phosphate or with tris(2,3

dibromopropyl)` phosphate, using a quantity of one of said `phosphates equal to 4.0% by weight of the polystyrene.

The resulting blends were extruded and pelletelized on a l12-extruder at 375 F. The blend which contained the bis(2bomoethyl) 2chloroethyl phosphate was molded `at 500 F. into physical test specimens on anS-oz. Reed Yinjection mol'dinigrmahine to give colorless, molded test specimens. Under the same conditions, the blend which the tlis(2,3-dibromopropyl)v phosphate could not be molded a tall lowing Yto excessive carbonization and Vincreased fluidity.l

The molded specimens were tested for flame-retardance as follows: The specimens were subjected to repeated (3) ignition with Ya Bunse-n burner flame for 10 second periods in a draft-free hood. After each ignitioniperiod,.upon removal of the flame, the specimens were found to be self-extinguishing in less than 5 seconds after removal of flame, whereas a control test specimen, i.e., a similarly molded polystyrene which did not contain an additive, continued ,to burn rapidly, drip flame, and emit heavy I #black smoke after the iirst ignition period. The bis(2 bromoethyl) 2-chloroethyl phosphate had thus rendered j to` theburning test described above, the specimens from all three blends were found to -be self-extinguishing.

i Example 1I i "lffhe following compounds were tested for llame-retardant effect on rigid polyurethane foams.

(il) i Bis(2brornoethyl) 2-chloroethyl phosphate (Il) 2-bromoethyl 2-bromopropyl 2-chloropropyl phosphate (HI) 2-bromoethyl 2,3-dichloropropyl 2-brom-3-chlorotainedwas warmed to 45 C., and 1.0 yg. of titanium tetgaehlorjde was added to serve as catalystfor subsequent reaction with ethylene oxide. The mixture of phosphorobromidochloridate and catalyst was treated Iwith 570 g.

, (12.9 moles) of ethylene oxide ,du-ring 1.25 hours while maintaining the temperature of the reaction mixture at 60-55 C. during addition of about one-half of the ethyl'- ene oxide and allowing the temperature to increase gradually to 102 C. while the remainder of the oxide was added. The whole was then warmed at reflux (102408 E"(2.) for 0.5i hourV and nally' concentrated to 100 C./1--

mm. to 4give as residue 2124 g. of the crude bis(2bromo propyl phosphate Testing was conducted using the following formulation:

. Parts by weight '2,4-toluylene diisocyanate 36.60 Polyether triol` 63.40 Trichlorouoromethane (Freon 1l) 12.60 Silicone oil (Dow-Corning, 500 Fluid) 0.30

' Tin catalyst' 0.03

A One of the above phosphates A, 10.00

The above formulations were lstirred thoroughly, poured into moldsand allowedto set to rigid foams atv room temperature.` Testing ofthe resulting hardened, rigid foams for ilame-retardance,` employing the American So- .ciety for Testing Materials procedure, Tentative Method of Test for Flammability of Plastic Foams and sheeting,"

tg Y

designation D1692-59T, showed all of the specimens to have been rendered llame-retardant, whereas the contro i.e., a hardened, rigid foam prepared from formulations containing all of the above constituents in the same quantities except that no phosphate was present, burned vigorously after being removed from the Vflame until they were completely consumed.

The hardened foams prepared above were Aalso tested for resistance to humidity by maintaining them for one Week in a chamber at 72 C. and 95% relative humidity, and then testing their mechanical strength, employing the American Society for Testing Materials procedure, Tentative Methtod of Test for Compressive Strength of Rigid Cellular Plastics, designation Dl621-59T. TheV following instrument readings were obtained on discs (2 diameter, 11/2" thickness) of the hardened, rigid foams.

Additive: Load, lbs. I 114 LII 126 III 132 Control 106 Since the quantity of the present phosphate which is employed with the polymeric material will vary with the adjuvant effect sought, with the nature of the polymer and the nature of the individual phosphate, it is evident made to accommodate different requirements. .The same processes as illustrated in the above examples have been found to be satisfactory for employing different vinyl polymers, or different condensation polymers than vthose used in theexamples.

Although they present phosphates confer a variety ofbenecial properties to polymeric materials, they may be used with other additives which are customarily employed as adjuvants for polymeric materials. Inasmuch as the present phosphates are substantially unreactive with the usual, commerciallyV available polymer adjuvants, the use of such adjuvants with the phosphates is permissible and in many instances is desirable, e.g., illers, dyes, Vcrosslinking agents, foam-producing agents, fungicides, etc. may be used, Y Y

Polymeric materials containing the presently provided mixed phosphates maybe molded, extruded, ycalendered, spread, or sprayed. Typical applications for the materials include molded, cast or extruded objects, continuous sheetings, tubing, iibers, films, wire coatings, textile coatings, laminates, paints, varnishes and enamels, wood preservatives, adhesives, and caulking compounds.

Other modes of applying the principles of this invention -may be employed instead of those specifically set forth above, changes being made as regards'the details herein disclosed, provided the elements set forth in any of the following claims or equivalents thereof be employed.

What Awe Vclaim is:

Y 1. 2bromoethyl 2-bromopropyl 2-chloropropyl phos- 2. 3-bromo-Z,Z-dimethylpropyl 2chloropropy1 2-bromopropyl phosphate. y

, `3. 3-bromo-2,2dimethylpropyl phosphorobromidochloridate.

4. 3-bromo-2,Z-dimethylpropyl 2-bromo-3-butenyl 2- chloro-3butenyl phosphate. Y

5. The method of preparing phosphates containing Vphates and quantities employed in the examples can be both chlorine and bromine which comprises bromine a cyclic phosphorus compound of the formula Y l? v R lo 0\ [R/CR']n roi R-(lJ-O R wherein R is selected from the class'consisting of hydrogen and alkyl of from 1 to 2 carbon atoms and haloalkyl of from 1 to 2 carbon atoms,fR is selected from the class consisting of hydrogen and alkyl of from'l to 5 carbon atoms and haloalkyl of from l to 5 carbon atoms, and n is zero or one, until cessation of bromine discolorization, and then contacting the resulting reaction product with an oxirane compound of the formula Hzo--GH-R" in which R is selected from the class consisting of hydrogen, alkyl of from 1 to 5 carbon atoms and haloalkyl wherein R is selected from the .class consisting of hydrogen and alkyl of from 1 to 2 carbon atoms and haloalkyl of from l to 2 carbon atoms, R is selected from the class consisting of hydrogen and alkyl of from 1 to 5 carbon atoms and haloalkyl of from l to Scarbon atoms, and n is zero or one. Y

7. The method which comprises treating 2-chloro-1,3,2 dioxaphospholane with bromine until cessation of bromine decoloriza'tion and reacting the resulting reaction product with ethylene oxide to give bis(2bromoethyl) 2-chloroethyl phosphate.'

8. The method which comprises reacting 2chlorol,3,2

Ydioxaphospholane with bromine to give 2-bromoethyl phosphorobrornidochloridate.

9. Themethod which comprises mixing together phosphorous trichloride with ardiolof the formula where R is selected from the class consisting of hydrogen and alkyl of from 1 to 2 carbon atoms and haloalkyl of from l to 2 carbon atoms, R is selected from the class consisting of hydrogen and alkyl of from l to 5 carbon Htc-orr-R/ K o where R" is selected from the class consisting of hydrogen,

alkyl of from l to 5 carbon atoms and haloalkyl of from l to 5 carbon atoms and vinyl, propenyl, propynyl, phetreating with i Y oxyniethyl, and cyclohexyloxymethyl to give a mixed Y phosphate of the formula R `R' R o RMR" m oiloHHBr i', if' 11 0mm 11,1"

were yYR, R', R" and n are as defined above.

f 10. The method which comprises reacting 2-ch1oro-5,5

dimethyl-1,3,2-dioXaphosphorinane with bromine to give 3bromo-2,2#dimethylpropy1 phosphorobromidochloridate. 11.V The method which comprises reacting 2`ch1oro4 (chloromethyl)1,3,2dioxaphospho1ane with bromine to give 2bromo-1-(ch1oromethy1)ethyl phosphorobromidochloridate and 2-bromo-3-ch1oropropy1 phosphorobromidochloridate.

, l Y 22 12. 2-b1omo-1-(chloromethyDethyl 2-bromo-3-phenoxypropyl 2-.ch1oro-3-phenoxypropy1 phosphate together with minor amounts of isomeric phosphate esters.

References Cited inthe lfile of this patent Rafelson et al. Nov.` 28, 1961 UNITED STATES PATENT oEEICE CERTIFICATE 0F CORRECTION Patent No. 3, 132, 169 May 5, 1964 Gail H Birum et al.,

'lt is hereby certified that enf-Tor appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 8, line 39, for "dimensoinal" read dimensional column 17, in the table, under athe heading "Calcyd for CHl2Br2C1O4P.", line 3 thereof, for "'475" read 42,75

same column 17, line 49, for v'HQPOQLM read H3PO4-; column 18, line 22, for a tall" read. at all Signed and sealed this 8th day of December 1964,7

IRNEST W. SWIDER t EDWARD J. BRENNER .ttesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTIoN Patent No. 3, 132, 169 May 5Y 1964 v e311 H., Birum et a1.,

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 8, line 39, for ""dmensoinal read dimensional column 17, in the tableq under nthe heading "Caldd for CH12Br2ClO4P.", line 3 thereofY for "4;75 read 4275 ng same Column l7 line 49Y for "H2PO4" read H3PO4-; Column 18, line 22Y for ."3 tall read. at all Signed and Sealed this 8th day of December 1964Q SEAL) :Hest:

RNEST W. SWIDER' EDWARD J. BRENNER ttesting Officer Commissioner of Patents 

1. 2-BROMOETHYL 2-BROMOPROPYL 2-CHLOROPROPYL PHOSPHATE.
 3. 3-BROMO-2,2-DIMETHYLPROPYL PHOSPHOROBROMIDOCHLORIDATE.
 6. THE METHOD OF PREPARING PHOSPHOROBROMIDOCHLORIDATES WHICH COMPRISES TREATING WITH BROMINE A CYCLIC COMPOUND OF PHOSPHORUS OF THE FORMULA 